Film-forming material mixed-gas forming device and film forming device

ABSTRACT

There is provided a film-forming material mixed-gas forming device including: a film-forming material supply unit that supplies a film-forming material in liquid form at a predetermined flow rate; a carrier gas supply unit that supplies a carrier gas at a predetermined flow rate; a main vaporization unit that vaporizes the film-forming material by heating the film-forming material supplied from the film-forming material supply unit and the carrier gas supplied from the carrier gas supply unit; and an auxiliary vaporization unit having a porous vaporization member which captures carried over droplets of the film-forming material in gas flowing out from the main vaporization unit and vaporizes the captured droplets of the film-forming material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No. 62/890,041, filed on Aug. 21, 2019, in the United States Patent and Trademark Office, the disclosure of which is incorporated herein in its entirety by reference.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a film-forming material mixed-gas forming device and a film forming device.

Related Art

The film-forming technique of forming a desired material layer on a base substrate is widely used when manufacturing semiconductor devices or the like. For example, a film-forming material, which is in liquid phase at room temperature and atmospheric pressure and contains atoms forming at least part of the material laminated on a semiconductor substrate, may be used. Examples of such a film-forming material in liquid form include triethoxysilane (TEOS) used to form a SiO₂ insulating film. If the film-forming material in liquid form is used, a device is required which vaporizes the film-forming material to thereby supply the vaporized film-forming material and a carrier gas to a reaction chamber.

For example, U.S. Pat. No. 6,210,485 discloses a device that quantitatively supplies a film-forming material in liquid form (liquid precursor substance) and a carrier gas, vaporizes the supplied film-forming material, mixes the vaporized film-forming material with the carrier gas, and supplies a mixed gas of the vaporized film-forming material and the carrier gas to a reaction chamber.

SUMMARY OF THE INVENTION

In a case of forming a thick film, a large amount of a film-forming material is desirably supplied to improve production efficiency. However, in a case of using a film-forming material in liquid form at room temperature and atmospheric pressure, such a large amount of the film-forming material may possibly lead to insufficient vaporization of the film-forming material. If the film-forming material is insufficiently vaporized, droplets of the film-forming material are carried over to the reaction chamber and are attached to a surface of the substrate. This may possibly cause degradation in the quality of a formed film. Therefore, it is desirable to use a film-forming material mixed-gas forming device and a film forming device which are capable of reliably vaporizing the film-forming material.

According to an aspect of the present disclosure, there is provided a film-forming material mixed-gas forming device including: a film-forming material supply unit that supplies a film-forming material in liquid form at a predetermined flow rate; a carrier gas supply unit that supplies a carrier gas at a predetermined flow rate; a main vaporization unit that vaporizes the film-forming material by heating the film-forming material supplied from the film-forming material supply unit and the carrier gas supplied from the carrier gas supply unit; and an auxiliary vaporization unit having a porous vaporization member which captures carried over droplets of the film-forming material in gas flowing out from the main vaporization unit and vaporizes the captured droplets of the film-forming material.

In the film-forming material mixed-gas forming device according to the aspect of the present disclosure, the porous vaporization member may be formed of a sintered metallic body.

In the film-forming material mixed-gas forming device according to the aspect of the present disclosure, the sintered metallic body may be formed of a fibrous sintered metallic body.

The film-forming material mixed-gas forming device according to the aspect of the present disclosure may further include an auxiliary heater that heats the auxiliary vaporization unit.

In the film-forming material mixed-gas forming device according to the aspect of the present disclosure, the auxiliary vaporization unit may be provided adjacent to the main vaporization unit.

The film-forming material mixed-gas forming device according to the aspect of the present disclosure may further include a second material gas supply unit that supplies a second material gas to a location downstream of the auxiliary vaporization unit at a predetermined flow rate.

According to another aspect of the present disclosure, there is provided a film forming device including: the film-forming material mixed-gas forming device according to one aspect; and a reaction chamber to which the film-forming material and the carrier gas are supplied from the film-forming material mixed-gas forming device.

The film-forming material mixed-gas forming device and the film forming device according to one aspect of the present disclosure are capable of reliably vaporizing the film-forming material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram illustrating a configuration of a film forming device according to an embodiment of the present disclosure.

DETAILED DESCRIPTION OF THE INVENTION

Hereinbelow, an embodiment of the present disclosure will be described with reference to the drawing. FIG. 1 is a schematic diagram illustrating a configuration of a film forming device 100.

The film forming device 100 includes a film-forming material mixed-gas forming device 1 according to the embodiment of the present disclosure, a film-forming material supply 2, a carrier gas supply 3, a second material gas supply 4, and a reaction chamber 5. The film-forming material supply 2 supplies a film-forming material R1 to the film-forming material mixed-gas forming device 1. The carrier gas supply 3 supplies a carrier gas C to the film-forming material mixed-gas forming device 1. The second material gas supply 4 supplies a second material gas R2 to the film-forming material mixed-gas forming device 1. A film-forming material mixed gas Gm, which is a mixed gas of the vaporized film-forming material R1, the carrier gas C, and the second material gas R2, is supplied from the film-forming material mixed-gas forming device 1 to the reaction chamber 5.

The film-forming material mixed-gas forming device 1 includes a film-forming material supply unit 11, a carrier gas supply unit 12, a main vaporization unit 13, an auxiliary vaporization unit 14, an auxiliary heater 15, an outflow valve 16, and a second material gas supply unit 17. The film-forming material supply unit 11 supplies the film-forming material R1 in liquid form at a predetermined flow rate. The carrier gas supply unit 12 supplies the carrier gas C at a predetermined flow rate. The main vaporization unit 13 vaporizes the film-forming material R1 by heating the film-forming material R1 supplied from the film-forming material supply unit 11 and the carrier gas C supplied from the carrier gas supply unit 12, and forms a preliminary mixed gas Gp which is a mixed gas of the vaporized film-forming material R1 and the carrier gas C. The auxiliary vaporization unit 14 captures carried over droplets of the film-forming material R1 in the preliminary mixed gas Gp flowing out from the main vaporization unit, and vaporizes the captured droplets of the film-forming material R1. The auxiliary heater 15 heats the auxiliary vaporization unit 14. The outflow valve 16 is capable of stopping an outflow of the preliminary mixed gas Gp. The second material gas supply unit 17 is provided downstream of the auxiliary vaporization unit 14, and supplies the second material gas R2 at a predetermined flow rate.

The film-forming material supply unit 11 regulates the flow rate of the film-forming material R1, which is supplied from the film-forming material supply 2, at the predetermined flow rate in advance. The film-forming material supply unit 11 may be configured to have a flow rate sensor and a flow rate regulating valve. The film-forming material R1 is selected depending on the material of a film to be formed, and, for example, triethoxysilane (TEOS) is used as the film-forming material R1.

The carrier gas supply unit 12 regulates the flow rate of the carrier gas C, which is supplied from the carrier gas supply 3, at the predetermined flow rate in advance. The carrier gas supply unit 12 can be configured to have a flow rate sensor and a flow rate regulating valve. Inert gas such as helium, argon or nitrogen is used as the carrier gas C.

The main vaporization unit 13 vaporizes the film-forming material R1 by heating the film-forming material R1 and the carrier gas C which have been supplied. For this reason, the main vaporization unit 13 can be configured to have a heat source, for example, an electric heater. In addition, the main vaporization unit 13 preferably has a heat transfer structure capable of transferring sufficient heat to the film-forming material R1 supplied from the film-forming material supply unit 11, and to the carrier gas C supplied from the carrier gas supply unit 12. The heated temperature of the main vaporization unit 13 is preferably greater than or equal to the boiling point of the film-forming material R1, more preferably a temperature greater by 5° C. to 20° C. than the boiling point of the film-forming material R1.

In addition, the main vaporization unit 13 may be configured to generate a gas flow, for example, a swirl gas in flows of the carrier gas C, which is capable of facilitating the vaporization of the film-forming material R1 by shearing and breaking up the film-forming material R1 in liquid form.

The auxiliary vaporization unit 14 has a porous vaporization member 141 formed of a porous body having pores which prevents droplets of the film-forming material R1 from passing therethrough. The porous vaporization member 141 prevents droplets of the film-forming material R1 from being introduced into the reaction chamber 5 by capturing the droplets of the film-forming material R1 contained in the preliminary mixed gas Gp flowing out from the main vaporization unit 13. In addition, since the droplets of the film-forming material R1 captured by the porous vaporization member 141 penetrate into the porous vaporization member 141, the area of contact between the porous vaporization member 141 and the preliminary mixed gas Gp passing therethrough becomes large, the residence time in the member 141 become longer and thus the vaporization of the preliminary mixed gas Gp becomes facilitated.

Since the preliminary mixed gas Gp flowing out from the main vaporization unit 13 has been heated in the main vaporization unit 13, it is considered that the preliminary mixed gas Gp has thermal energy enough to vaporize the droplets of the film-forming material R1 contained therein. For this reason, when the droplets of the film-forming material R1 stay inside the auxiliary vaporization unit 14, the film-forming material R1 in liquid phase can be vaporized by the heat contained in both of the film-forming material R1 in gaseous phase and the carrier gas.

In more detail, when the saturated vapor pressure of the liquid of the film-forming material R1 captured by the auxiliary vaporization unit 14 is greater than the partial vapor pressure of the film-forming material R1 in the preliminary mixed gas Gp passing through the auxiliary vaporization unit 14, the liquid of the film-forming material R1 captured by the auxiliary vaporization unit 14 can be vaporized. If the amount of film-forming material R1 vaporizing in the auxiliary vaporization unit 14 is greater than the amount of the liquid of the film-forming material R1 newly flowing out from the main vaporization unit 13, it is possible to attain an equilibrium state where the film-forming material mixed gas Gm containing a predetermined amount of film-forming material R1 is formed while preventing the auxiliary vaporization unit 14 from being blocked.

A sintered metallic body is preferably used as the porous body forming the porous vaporization member 141 of the auxiliary vaporization unit 14. If the porous vaporization member 141 is formed of the sintered metallic body, since it is possible to increase the thermal conductivity of the porous vaporization member 141, the captured droplets of the film-forming material R1 can be rapidly vaporized owing to heat being transferred thereto. A chemically stable metal such as stainless steel is preferably used as metal forming the porous vaporization member 141.

In addition, a fibrous sintered metallic body is preferably used as the sintered metallic body forming the porous vaporization member 141. It is possible to increase the porosity of the fibrous sintered metallic body while reducing the pore diameters of the fibrous sintered metallic body. This makes it possible to reduce passing resistance of the preliminary mixed gas Gp while reliably preventing the droplets of the film-forming material R1 from passing through the porous vaporization member 141, thereby rapidly vaporizing the captured film-forming material R1. It is desirable that the filtration accuracy of the porous vaporization member 141 be, for example, less than or equal to 0.5 μm. Furthermore, it is possible to improve a vaporization capability (the vaporized amount of film-forming material R1 per unit time) of the porous vaporization member 141 by increasing the volume of the porous vaporization member 141. As described above, since the vaporization capability of the porous vaporization member 141 depends on various conditions, it is possible to determine specifications of the porous vaporization member 141 by experiments or an actual operation.

The auxiliary vaporization unit 14 can be configured to have a flange 142 for fixing the porous vaporization member 141 in a flow path. The porous vaporization member 141 can be formed into the shape of a tube having one sealed end and the other end that is connected to the flange 142. If the porous vaporization member 141 and the flanges 142 are formed of metal, it is possible to rapidly vaporize the captured droplets of the film-forming material R1 by conducting heat of the auxiliary heater 15 to the porous vaporization member 141. In addition, if the auxiliary vaporization unit 14 is configured such that the flange 142 is provided at one end of the porous vaporization member 141 having a tubular shape, the auxiliary vaporization unit 14 can be configured such that the porous vaporization member 141 is disposed in the interior of an inlet flow path or the like of the outflow valve 16. Therefore, since the auxiliary vaporization unit 14 does not require a dedicated housing, it is possible to reduce the size of the film-forming material mixed-gas forming device 1.

It is preferable that the auxiliary vaporization unit 14 is provided adjacent to the main vaporization unit 13. In the present embodiment, branches or other devices are not provided in a passage between the main vaporization unit 13 and the auxiliary vaporization unit 14. This makes it possible for the auxiliary vaporization unit 14 to facilitate the vaporization of the droplets of the film-forming material R1, which are captured by the porous vaporization member 141, by making efficient use of thermal energy of the preliminary mixed gas Gp flowing out from the main vaporization unit 13.

The auxiliary heater 15 is provided so as to directly heat the auxiliary vaporization unit 14, or to indirectly heat the auxiliary vaporization unit 14 by heating a configuration element in the vicinity of the auxiliary vaporization unit 14. As described above, the preliminary mixed gas Gp flowing out from the main vaporization unit 13 to the auxiliary vaporization unit 14 has sufficient heat. For this reason, the heating temperature of the auxiliary heater 15 only has to be set such that the auxiliary heater 15 is capable of preventing a decrease in the temperature of the auxiliary vaporization unit 14, which is caused by heat radiation to the ambient atmosphere. Therefore, the heating temperature may be less than the boiling point of the film-forming material. Specifically, the heating temperature of the auxiliary heater 15 can be set less than by approximately 20° C. to 40° C. than the boiling point of the film-forming material.

In accordance with an operation mode of the reaction chamber 5, the outflow valve 16 selects whether the preliminary mixed gas Gp is supplied or the supply of the preliminary mixed gas Gp is stopped. In addition, the outflow valve 16 can be used to stabilize the vaporization of the film-forming material R1 by applying a proper back pressure to the main vaporization unit 13.

The second material gas supply unit 17 further adds the second material gas R2 to the preliminary mixed gas Gp flowing out from the outflow valve 16. This allows the film-forming material mixed gas Gm, which is a mixed gas of the preliminary mixed gas Gp and the second material gas R2, to be formed. The film-forming material mixed-gas forming device 1 of the present embodiment supplies the film-forming material mixed gas Gm, which is formed in this manner, to the reaction chamber 5.

The second material gas supply unit 17 can be configured to have a flow rate sensor and a flow rate regulating valve. The second material gas supply unit 17 mixes the preliminary mixed gas Gp with the second material gas R2, after the complete vaporization of the film-forming material R1 by the auxiliary vaporization unit 14. The temperature of the second material gas R2 may be lower than that of the preliminary mixed gas Gp. This makes it possible for the film-forming material mixed-gas forming device 1 to vaporize the film-forming material R1 in liquid form by making efficient use of heat of the main vaporization unit 13. It should be noted that the temperature of the second material gas R2 is set so as to prevent the vapor of the film-forming material from being condensed during mixing. For example, oxygen, argon, helium, or nitrogen gas is used as the second material gas R2.

The film-forming material supply 2 is configured so as to be capable of supplying the film-forming material R1 in liquid form at a pressure where the film-forming material R1 can be introduced into the film-forming material mixed-gas forming device 1 against the internal pressure thereof. As a specific example, the film-forming material supply 2 can be configured to include a sealed container 21 that stores the film-forming material R1 in liquid phase, and a pressurizing mechanism 22 that introduces pressurizing gas for pressurizing the film-forming material R1 into a head space inside the sealed container 21.

The sealed container 21 can be configured such that a pipe is connected to a lower portion of the sealed container 21, from which the film-forming material R1 is allowed to flow out. The pressurizing mechanism 22 can be configured to have a pressurizing gas cylinder 221 that stores the pressurizing gas, and a pressurizing gas regulating valve 222 that regulates the pressure of the pressurizing gas supplied from the pressurizing gas cylinder 221 to the sealed container 21. It is preferable that inert gas such as helium gas is used as the pressurizing gas.

The carrier gas supply 3 can be configured to have a carrier gas cylinder 31 that stores the carrier gas C, and a carrier gas regulating valve 32 that regulates the pressure of the carrier gas C supplied from the carrier gas cylinder 31 to the film-forming material mixed-gas forming device 1.

The second material gas supply 4 can be configured to have a second material gas cylinder 41 that stores the second material gas R2, and a second material gas regulating valve 42 that regulates the pressure of the second material gas R2 supplied from the second material gas cylinder 41 to the film-forming material mixed-gas forming device 1.

The reaction chamber 5 is configured such that the base substrate, on which a film is formed using the film-forming material mixed gas, is accommodated in the reaction chamber 5 and the internal space of the reaction chamber 5 can be vacuumed. The reaction chamber 5 is capable of having a well-known configuration having an auxiliary device for forming a film, for example, a plasma generator.

As described above, the film-forming material mixed-gas forming device 1 and the film forming device 100 including the film-forming material mixed-gas forming device 1 include the auxiliary vaporization unit 14, thereby capturing and vaporizing droplets of the film-forming material R1 contained in the gas flowing out from the main vaporization unit 13. This makes it possible to improve film-forming quality by preventing the droplets of the film-forming material R1 from being introduced into the reaction chamber 5.

The embodiment of the present disclosure has been described above; however, the present disclosure is not limited to the foregoing embodiment. In addition, the effects in the above-described embodiment have been described merely as an example of the most suitable effects of the present disclosure, and the effects of the present disclosure are not limited to those in the above-described embodiment.

For example, in the film-forming material mixed-gas forming device according to the present disclosure, the auxiliary heater 15, the outflow valve 16, and the second material gas supply unit 17 are optional configuration elements, which may be omitted. In addition, in the film-forming material mixed-gas forming device 1 according to the present disclosure, the auxiliary vaporization unit 14 may be provided downstream of a merging point between the outflow valve 16 and the second material gas supply unit 17.

EXAMPLES

Using the film forming device having the configuration of FIG. 1 , all gases were supplied to the reaction chamber in which a wafer was loaded. Thereafter, the number of particles attached to a surface of the wafer inside the reaction chamber was measured in each range. For comparison, the same test was conducted using a film forming device having the same configuration except that the porous vaporization member of the auxiliary vaporization unit was removed. It should be noted that the porous vaporization member of the auxiliary vaporization unit, which was formed of a fibrous sintered stainless steel body and was formed into the shape of a tube having one sealed end, was used.

Triethoxysilane was used as the film-forming material, and the supply amount of the film-forming material was 16.5 g/min. Argon gas was used as the carrier gas, and the supply amount of carrier gas was 10 slm. Oxygen gas was used as the second material gas, and the supply amount of second material gas was 40 slm. After the resultant mixed gas was supplied to the reaction chamber for 300 seconds, the number of particles attached to the surface of the wafer was counted. The following Table 1 shows the results of counting the number of particles.

TABLE 1 Number of particles [Piece] Number of particles [Piece] Particle size (Auxiliary vaporization unit (Auxiliary vaporization unit [μm] is not provided) is provided) 0.026-0.045 12533 35 0.045-0.06  1200 5 0.06-0.10 20 3 0.10-0.20 1 0 0.2-0.5 0 0 0.5-1.0 0 0 1.0< 1 2 Total 13755 45

As described above, it has been confirmed that it was possible to prevent the film-forming material in liquid phase from being carried over into the reaction chamber by vaporizing the film-forming material using the film-forming material mixed-gas forming device having the auxiliary vaporization unit. In addition, in maintenance after a long period of operation, it has been confirmed that no liquid was stored in the porous vaporization member, that is, all of the film-forming material in liquid form could be vaporized.

EXPLANATION OF REFERENCE NUMERALS

-   -   1 FILM-FORMING MATERIAL MIXED-GAS FORMING DEVICE     -   2 FILM-FORMING MATERIAL SUPPLY     -   3 CARRIER GAS SUPPLY     -   4 SECOND MATERIAL GAS SUPPLY     -   5 REACTION CHAMBER     -   11 FILM-FORMING MATERIAL SUPPLY UNIT     -   12 CARRIER GAS SUPPLY UNIT     -   13 MAIN VAPORIZATION UNIT     -   14 AUXILIARY VAPORIZATION UNIT     -   15 AUXILIARY HEATER     -   16 OUTFLOW VALVE     -   17 SECOND MATERIAL GAS SUPPLY UNIT     -   100 FILM FORMING DEVICE     -   141 POROUS VAPORIZATION MEMBER 

What is claimed is:
 1. A film-forming material mixed-gas forming device comprising: a film-forming material supply unit that supplies a film-forming material in liquid form at a predetermined flow rate; a carrier gas supply unit that supplies a carrier gas at a predetermined flow rate; a main vaporization unit that vaporizes the film-forming material by heating the film-forming material supplied from the film-forming material supply unit and the carrier gas supplied from the carrier gas supply unit, wherein the carrier gas and the film-forming material are mixed to form a mixed gas in the main vaporization unit; an auxiliary vaporization unit having a porous vaporization member which captures carried over droplets of the film-forming material in the mixed gas flowing out from the main vaporization unit and vaporizes the captured droplets of the film-forming material; and a second material gas supply unit that supplies a second material gas to a location downstream of the auxiliary vaporization unit at a predetermined flow rate, wherein the porous vaporization member comprises a porous body having pores, wherein the film-forming material mixed-gas forming device is configured to flow all of the mixed gas flowing out from the main vaporization unit through the porous vaporization member, wherein the main vaporization unit is heated to a temperature 5° C. to 20° C. greater than the boiling point of the film-forming material, and wherein the auxiliary vaporization unit is heated to a temperature 20° C. to 40° C. less than the boiling point of the film-forming material.
 2. The film-forming material mixed-gas forming device according to claim 1, wherein the porous vaporization member is formed of a sintered metallic body.
 3. The film-forming material mixed-gas forming device according to claim 2, wherein the sintered metallic body is formed of a fibrous sintered metallic body.
 4. The film-forming material mixed-gas forming device according to claim 1, further comprising an auxiliary heater that heats the auxiliary vaporization unit.
 5. The film-forming material mixed-gas forming device according to claim 1, wherein the auxiliary vaporization unit is provided adjacent to the main vaporization unit.
 6. The film-forming material mixed-gas forming device according to claim 1, wherein the carrier gas is a different gas than the second material gas.
 7. A film forming device comprising: the film-forming material mixed-gas forming device according to claim 1; and a reaction chamber to which the film-forming material and the carrier gas are supplied from the film-forming material mixed-gas forming device.
 8. The film-forming material mixed-gas forming device according to claim 1, wherein the carrier gas comprises helium, argon, or nitrogen.
 9. The film-forming material mixed-gas forming device according to claim 1, wherein the second material gas comprises helium, argon, nitrogen, or oxygen.
 10. The film-forming material mixed-gas forming device according to claim 1, wherein the main vaporization unit is heated to the boiling point of the film-forming material.
 11. The film-forming material mixed-gas forming device according to claim 1, wherein the porous vaporization member has a shape of a tube having one sealed end.
 12. The film-forming material mixed-gas forming device according to claim 1, further comprising: a film-forming material supply container that stores the film-forming material in liquid form; and a pressurizing mechanism configured to introduce a pressurizing gas into a head space of the film-forming material supply container.
 13. The film-forming material mixed-gas forming device according to claim 12, wherein the pressurizing mechanism comprises a pressurizing gas cylinder configured to store the pressurizing gas, and a pressurizing gas regulating valve configured to regulate the pressure of the pressurizing gas supplied from the pressurizing gas cylinder to the film-forming material supply container; and wherein the pressurizing gas is helium. 